JPH07175156A - Negative silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To provide the negative silver halide photographic emulsion capable of giving a silver halide photographic sensitive material high in sensitivity and small in fluctuation of sensitivity due to the time length of exposure and that between exposure and development. CONSTITUTION:The negative silver halide photographic emulsion comprises the silver halide grains composed of >=95 mol% silver chloride and has at least one kind of metal compound having one of metals of groups VIII, IX, X and XII of the periodic table, and Pb, Re, Mo, W, Cr, and gallium added during grain formation to the end of physical ripening and the total of the effective anion valences of these compounds are 0.9-1.35 times those of the effective cation valences, or this emulsion comprises the silver halide grains composed of >=95mol% silver chloride and has at least one kind of sulfur element or compound added during grain formation to the end of physical ripening.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative-working silver halide photographic emulsion capable of providing a silver halide photographic light-sensitive material having a high sensitivity and a small sensitivity fluctuation with exposure time and a small sensitivity fluctuation with time from exposure to development. Is.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials, particularly silver halide color photographic light-sensitive materials, are widely used today because of their high sensitivity, excellent gradation and sharpness.

However, the development processing of the silver halide color photographic light-sensitive material is a so-called wet processing, and it takes time to prepare the processing solution, it becomes dirty, a waste solution containing various chemicals is discharged, and a dark room is required. There are drawbacks such as a long time from the start of the operation until the first print is obtained. In order to make up for these drawbacks and make full use of the advantages of the silver halide color photographic light-sensitive material described above, until now, only a small number of large development laboratories have focused on the development of color negatives to the production of color prints. The scheme has been adopted.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic processors, improvements in developing solutions, improvements in silver halide color photographic light-sensitive materials and their packaging forms have been accumulated. Therefore, a so-called minilab, which is capable of consistently performing color negative development to color print production in a small space such as at a photo shop, is rapidly becoming popular.

In recent years, the development processing time has been remarkably shortened by employing a silver halide emulsion containing a high concentration of silver chloride. However, it has been known that a silver halide emulsion containing a high concentration of silver chloride has a drawback that it is difficult to obtain high sensitivity and that the reciprocity law failure is large.

It has been disclosed that the inclusion of a Group 8 to 10 metal compound can improve reciprocity law failure and increase sensitivity. In addition, Japanese Examined Patent Publication No.
50-23618, 52-18310, 58-15952, 59-21402
No. 8, No. 61-67845 and the like disclose that inclusion of a rhodium compound or an iridium compound can improve reciprocity law failure and enhance contrast. Although such a technique improves the reciprocity law failure of a silver halide emulsion containing a high concentration of silver chloride, it causes remarkable desensitization and the development density changes with the lapse of time from the exposure of the light-sensitive material to the processing thereof. There was a drawback. Tokusho
No. 48-35373 describes that a black-and-white photographic paper with high contrast can be obtained at a low price by including a water-soluble iron compound in a silver chloride emulsion. However, this technique has a drawback that the sensitivity changes greatly due to temperature changes during exposure. Kohei
4-335341, JP-A-5-127281, by containing a specific sulfur group element together with the iron compound by the end of physical ripening of the particles, sensitivity fluctuation due to temperature change during exposure, especially high illuminance It is described that sensitivity fluctuation due to temperature change during exposure is improved. In this publication, there is no description about the preferable addition amount ratio of the iron compound and the sulfur group compound, and the iron compound: sulfur group compound is about 10: 1 and about 1: 1.5 in terms of the compound molar ratio.
There is only a description used in. Further, there is no description about metals other than iron compounds.

Although these techniques improve sensitivity fluctuations due to temperature changes, they have not solved the problem of low sensitivity and large sensitivity fluctuations due to the time from exposure to development.

The method of chemically sensitizing by adding a sulfur group element during grain formation is well known as a method for directly preparing a positive emulsion. Japanese Patent Laid-Open Nos. 5-103353 and 5-107683 disclose a technique of incorporating a specific metal in a positive emulsion. In these techniques, the sulfur group compound is added during the grain formation, but the grain formation is stopped once, and the chemical sensitization is performed by raising the temperature after the addition of the sulfur group compound and before the grain formation is restarted. There is a process to do. Also, the emulsion used is a silver bromide emulsion, a direct positive emulsion,
It did not suggest any solution to the problem that the sensitivity was large in the negative type high silver chloride emulsion in which the metal compound was added during the grain formation and the sensitivity varied greatly with the time from exposure to development.

[0009]

In contrast to the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity and has little sensitivity fluctuation due to exposure time and sensitivity fluctuation due to time from exposure to development. The object is to provide a negative-working silver halide photographic emulsion capable of providing a material.

[0010]

The inventors of the present invention have made intensive studies on silver halide photographic emulsions used in silver halide photographic light-sensitive materials, and found that the above-mentioned objects of the present invention can be achieved by the following constitutions. The present invention has been completed.

(1) At least one compound is added by the time physical ripening of silver halide grains is completed, and at least one of the compounds is a metal of Group 8 to 10 of the periodic table.
A metal compound containing a Group 12 transition metal, lead, rhenium, molybdenum, tungsten, chromium, and gallium, and the total effective anion valence of the added compound is 0.9 times or more and 1.35 times the total effective cation valence. A negative-type silver halide photographic emulsion characterized by containing the following silver halide grains.

(2) It is characterized in that at least 95 mol% is composed of silver chloride, and at least one elemental substance or compound of the sulfur group element is added by the end of physical ripening in the formation of silver halide grains. The negative type silver halide photographic emulsion as described in the above item (1).

The present invention will be described in detail below.

The composition of the silver halide photographic emulsion according to the present invention may have any halogen composition such as silver chloride, silver chlorobromide and silver chloroiodobromide, but silver chloride is 95 mol%.
The above-mentioned silver chlorobromide containing substantially no silver iodide is preferable. The content of silver chloride is preferably 97 mol% or more,
It is more preferably 98 to 99.9 mol%.
The high silver chloride emulsion referred to in the present invention is a silver chlorobromide emulsion containing 95 mol% or more of silver chloride and substantially containing no silver iodide.

The composition of the silver halide emulsion may be uniform or may have a portion containing a high concentration of silver bromide. In this case, the portion containing silver bromide in a high concentration may be either epitaxy bonded to the silver halide emulsion grains or a so-called core-shell emulsion, or may not form a complete layer and may be partially formed. There may be only regions having different compositions. The composition may change continuously or discontinuously. The portion having a high concentration of silver bromide may be on the surface of the silver halide grain or on the inside thereof, but is preferably on the surface of the silver halide grain. The silver bromide content of the portion containing silver bromide in a high concentration is 10 mol% or more, preferably
20 to 50 mol%.

The total effective anion valency of the compound added during the physical ripening of the silver halide grain formation according to the present invention is added during the physical ripening of the silver halide grain formation. It is the total of the effective anion valences of each compound multiplied by the addition amount. As for the effective anion valence of a compound, when the compound is an ion-binding compound, the total of the valences of the polyvalent anions constituting the compound is taken as the effective anion valence. When the compound is a complex, it is the sum of the values obtained by multiplying the ionic valence of a ligand having a valence of 2 or more by the number of ligands.
The effective anion valency is 0 when the compound is other than an ion-binding compound or complex and the compound does not decompose to form a halide or a silver salt by the end of physical ripening in the formation of silver halide grains. . However, when the compound is a metal compound containing a metal of Group 8 to 10 of the periodic table, a transition metal of Group 12 of the periodic table, lead, rhenium, molybdenum, tungsten, chromium, and gallium, a polyvalent atom bonded to the metal atom The total ion valence of the group is the effective anion valence. The valence of an atom group bound to a metal is a general ionic valence for that atom, for example, the 15th group of atoms in the periodic table has an anion valency of 3, the 16th group atom of the periodic table has an anion valence. Is calculated as 2.

When the compound is other than the ion-binding compound and the complex and the compound is decomposed by the completion of the physical ripening of the silver halide grain formation, the element simple substance, the ion-binding compound (halide or silver salt), the complex When other compounds are formed, the effective anion valence of the compound to which the sum of the effective anion valences of the formed compounds is added. The effective anion valency of a compound formed by decomposition is the ionic valency of the compound in the ionic state in the case of a simple substance, the ionic valence of the ion in the case of an ion, and the anion valency of the silver salt in the case of a silver salt. The effective anion valence is the sum of the values obtained by multiplying only the multivalent valences of the ionic part by the number of atomic groups constituting the simple substance, ions and anion parts in the compound. The effective anion valence is 0 when the compound formed by decomposition is other than an ion-binding compound and a complex. However, when the compound generated by decomposition produces a compound that is sparingly soluble in silver, the total of the polyvalent valences of the atomic groups bonded to silver is taken as the effective anion valence of the compound.

The total effective cation valences of the compounds added during the physical ripening of the silver halide grain formation according to the present invention are added during the physical ripening of the silver halide grain formation. It is the sum of the effective cation valence of each compound multiplied by the amount added. When the compound is an ion-binding compound, the effective cation valence of the compound is defined as the sum of the valences of the polyvalent cations that compose the compound. When the compound is a complex, the sum of the value obtained by multiplying the ionic valence of the polyvalent central metal atom by the number of central metal atoms and the ionic valence of the polyvalent cation other than the central metal atom by the number of cations. Ask in.

When the compound is other than the ion-binding compound and complex and the compound is not decomposed to form a halide or a silver salt by the end of physical ripening in the formation of silver halide grains, the effective cation valence is It is 0. However, the compound is a group 8-10 metal of the periodic table, a group 12 transition metal, lead,
In the case of a metal compound containing rhenium, molybdenum, tungsten, chromium, and gallium, it is determined by the sum of the valence of the metal atom and the number of other polyvalent cations. When the compound is not an ion-binding compound or complex and the compound decomposes by the end of physical ripening for silver halide grain formation, the element simple substance, an ion-binding compound (halide or silver salt), complex, etc. In the case of preparing the compound (1), the effective cation valence of the compound to which the sum of the effective cation valences of the formed compounds is added. The effective cation valency of a compound formed by decomposition is the ionic valency of the compound in the ionic state in the case of a simple substance, the ionic valence of the ion in the case of an ion, and the cation valence forming a halide salt in the case of a silver salt. The effective cation valence is the sum of the values obtained by multiplying only the valences of the ionic part having a high valence by the number of atomic groups constituting the cation in the compound.

However, when the cation portion is a monovalent cation, it is excluded. The effective cation valence is set to 0 when the compound formed by decomposition is other than the ion-binding compound and the complex.

The total number of effective anion valences according to the present invention is 0.9 times or more and 1.35 times or less of the total number of effective cations. It is preferably 0.95 times or more and 1.3 times or more, and more preferably 1.0 times or more and 1.3 times or less.

At least one of the compounds added before the physical ripening of the silver halide grains according to the present invention is completed.
Species include metals of groups 8-10 of the periodic table, transition metals of group 12, lead,
It is a metal compound containing rhenium, molybdenum, tungsten, chromium, and gallium, and is added in the form of a metal ion salt or a complex salt mainly composed of metal ions. When the metal compound is a complex, cyanide is used as its ligand,
Thiocyanate ion, cyanate ion, chloride ion,
Examples thereof include bromide ion, iodide ion, carbonyl and ammonia. Among them, cyanide ion,
Thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

The metal compounds that can be preferably used in the silver halide emulsion according to the present invention, the number of effective anions and the number of effective cations per molecule are shown below, but the present invention is not limited thereto.

[0024]

[Table 1]

The addition of these metal compounds may be carried out by adding water, a water-miscible solvent such as methanol, ethanol, or a fluoroalcohol alone or by dissolving them in a mixed solvent. If it is poorly soluble in a suitable solvent, it may be added in the form of a dispersion. It may be added by dissolving it in a halide salt solution at the time of forming silver halide grains, or by dissolving it in a silver salt solution at the time of forming silver halide grains. Alternatively, silver halide fine particles containing a metal compound may be prepared in advance by the above-mentioned method, and the fine particles may be added by adding the fine particles.

The fine silver halide grains (meaning fine silver halide crystals, the same applies hereinafter) are usually 0.01 μm or more and 0.1 or more.
Particle size below μm, but below 0.01 μm or 0.1
Fine particles having a particle size of μm or more can also be used.

The halogen composition of these fine particles is silver chloride,
It may be either silver chlorobromide or silver bromide, and the composition thereof can be selected according to the distribution of silver bromide in the silver halide grains. The type of metal compound added is not particularly limited, but 2 to 4 types are preferable. The amount of the metal compound added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, particularly 1 × 10 ⁻⁸ mol, per mol of silver halide.
It is preferably not less than 5 mol and not more than 5 × 10 ^-5 mol.

As the compound added before the physical ripening in the formation of silver halide grains according to the present invention other than the above-mentioned metal compounds, any compound which does not interfere with the basic formation of silver halide grains can be used. . Compounds which do not interfere with the basic formation of silver halide grains do not include organic compounds used for the purpose of changing the shape of silver halide grains. The compound added in addition to the metal compound is a compound having an effective anion valency of 2 or more, for example, a salt of a sulfate ion and an alkali metal, a metal complex having ethylenediaminetetraacetic acid as a ligand, a simple substance of a sulfur group element. Alternatively, a compound or the like may be used, but a simple substance or compound of a sulfur group element is preferable.

The compounds of the sulfur group element added before the physical ripening of the silver halide grains according to the present invention are unstable compounds well known in the photographic science, that is, halides and silver salts. A compound that easily releases a sulfur, selenium or tellurium atom or an ion thereof after being added to the reaction system of. These compounds are U.S. Pat.Nos. 1,574,944 and 1,623,499,
No. 2,399,083, No. 3,297,446, No. 3,297,447
No. 3,320,069, No. 3,408,196, No. 3,442,65
No. 3, No. 3,402,670, No. 3,591,385, French Patent No. 2,093,038, No. 2,093,209, Japanese Patent Publication No. 52-34491
No. 52-34492, No. 53-295, No. 57-22090, JP
59-180536, 59-185330, 59-181337, 59-18
No. 7338, No. 59-192241, No. 60-150046, No. 60-151637
No. 61-246738, British Patent No. 255846, and No. 861984.
Issue and HESpencer et al., Journal of Photographic S
Cience magazine, 31 and 158-169 (1983) etc. can be used.

When a compound containing sulfur is used as the sulfur group element compound according to the present invention, it must be an unstable compound as described above. Therefore, even compounds containing sulfur and the like, compounds used as silver halide solvents such as thioether and tetra-substituted thiourea, compounds used as spectral sensitizing dyes such as thiocyanines, and heterocyclic mercapto compounds, etc. The compounds used as antifoggants are not included in the sulfur group compounds of the present invention.

Examples of the sulfur group element compounds containing sulfur include sodium thiosulfate, sodium sulfide, trisubstituted thioureas, thiocarbamides, allyl isocyanates, and thioformamides. As the sulfur group element compound containing selenium, isoselenocyanates,
Examples thereof include selenoureas, selenoketones, selenoamides, selenocarboxylic acids, selenoesters, diacyl selenides, selenophosphates and phosphine selenides. Examples of the sulfur-group element compound containing tellurium include tellurocarbamides, allyl isotellocyanates, and allyl telluroureas.

The sulfur group element simple substance and compound which can be preferably used in the silver halide emulsion according to the present invention and the number of effective anions and effective cations per molecule are shown below, but the present invention is not limited thereto. Not a thing.

[0033]

[Chemical 1]

[0034]

[Chemical 2]

[0035]

[Chemical 3]

[0036]

[Chemical 4]

[0037]

[Chemical 5]

[0038]

[Table 2]

The sulfur group element simple substance or compound may be added alone or by dissolving it in a water-miscible solvent such as water, methanol, ethanol, or fluoroalcohol, or by dissolving it in a mixed solvent. If it is poorly soluble in a suitable solvent, it may be added in the form of a dispersion. It may be added by dissolving it in a halide salt solution at the time of forming silver halide grains, or by dissolving it in a silver salt solution at the time of forming silver halide grains. Alternatively, silver halide fine particles containing a sulfur group element simple substance or a compound may be prepared in advance by the method described above, and the fine particles may be added by adding the fine particles. Alternatively, the silver halide fine particles may be added by preparing the silver halide fine particles obtained by adding these compounds and heat-treating after forming the silver halide fine particles and adding the fine particles. There is no particular limitation on the type of sulfur group element or compound to be added, but 2 to 4 types are preferable.

The amount of the sulfur group element simple substance or compound to be added to the silver halide emulsion is more preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly 1 × 10 ^-8 mol to 5 × 10 ^-5 mol or less.

The steps of preparing a silver halide emulsion include a nucleation step for forming nuclei of silver halide microcrystals, a subsequent crystal growth step, a physical ripening step, a desalting step for removing excess salts, and a photosensitive nucleus. The chemical / color sensitization step of forming and color sensitizing, and the chemical / color sensitization stopping step of stopping the formation of the photosensitive nucleus and the color sensitization. The silver halide emulsion is completed as a silver halide photographic light-sensitive material through a coating solution preparation step of preparing a coating solution suitable for coating, a coating step, and a subsequent drying step. The compound of the present invention may be added in any step until the end of physical ripening. It is preferably added in the crystal growth step and the physical ripening step, and more preferably in the physical ripening step. The compound of the present invention can be added so as to be contained in the silver halide grain in any distribution. That is, it may be added so as to be uniformly distributed in the particles, or may be added so as to be localized at a specific position.

The silver halide emulsion according to the present invention contains a metal of Group 8 to 10 of the periodic table, a transition metal of Group 12 of the periodic table, lead, rhenium,
A metal compound containing molybdenum, tungsten, chromium, or gallium and a sulfur group element simple substance or compound can be added. These compounds may be added so as to be distributed arbitrarily, or may be added at the same place, but it is preferable to add so as to be at the same place.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. Also,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Patent Publication No. 55-42737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39
(1973) etc., the octahedron,
Particles having a tetradecahedral shape, a dodecahedron shape, or the like can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grains according to the present invention is not particularly limited, but preferably 0.1 to 1.2 μm, more preferably 0.2 in view of other photographic properties such as rapid processability and sensitivity. The range is to 1.0 μm. The particle diameter can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page, 1955) or "Theory of Photographic Processes, 3rd Edition"
(Mies and James, co-authored, Chapter 2, Macmillan, 1966).

This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.
The monodisperse silver halide grains preferably have a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient representing the breadth of the particle size distribution and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area. As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one form of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor as disclosed in JP-A-57-92523 and 57-92524, published in Germany. An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

A known method can be used for chemically sensitizing the silver halide emulsion according to the present invention. That is, the sulfur sensitizing method, selenium sensitizing method, reduction sensitizing method, gold and other noble metal sensitizing methods can be used alone or in combination, but the gold sensitizing method is used alone or in combination with other sensitizing methods. It is preferable to use them in combination in order to obtain the effects of the present invention. As these chemical sensitizers, the sulfur group element simple substance and compound, and the metal compound added to the silver halide emulsion after the physical ripening step have the total number of effective anion valences and total number of effective cation valences of the present invention. Not involved in calculation.

Known sulfur sensitizers can be used in the silver halide emulsion according to the present invention.
For example, thiosulfate, allylthiocarbazide, thiourea,
Examples include α-sulfur, rilisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents 1,574,944, 2,410,689, 2,278,94
No. 7, No. 2,728,668, No. 3,501,313, No. 3,656,955,
West German application publication (OLS) 1,422,869, JP-A-56-24937,
The sulfur sensitizers described in JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is 1 × 10 ^-1 to 1 × per mol of silver halide. 10 ^-7 mol is preferred.

Known selenium sensitizers can be used in the silver halide emulsion according to the present invention. Aliphatic isoselencyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylates and esters, selenophosphates, diester selenides,
Selenides such as diethyl diselenide can be used, and specific examples thereof include U.S. Pat. Nos. 1,574,944 and 1,6
02,592 and 1,623,499. Known reduction sensitizers can be used for the silver halide emulsion according to the present invention. Examples thereof include stannous chloride, thiourea dioxide, hydrazine and polyamine.

Known gold sensitizers can be used for the silver halide emulsion according to the present invention. For example, it can be used as various other gold complexes such as chloroauric acid, gold sulfide, and gold thiosulfate, and examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. it can. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ per mol of silver halide.
It is preferably from mol to 1 × 10 ^-8 mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

The gold compound is preferably added to the silver halide emulsion after being dissolved in water or a water-miscible solvent such as methanol, ethanol or fluorinated alcohol, alone or in a mixed solvent. Further, in the case of a compound which is hardly soluble in a suitable solvent, it may be added in the form of a dispersion. The gold compound can be added at any time during the emulsion production process, but it is preferable to add the gold compound at the start of chemical ripening and during the process.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: (IIa-1) to (IIa-8) and (IIb) described on page 8 of the publication.
-1) to (IIb-7), 1- (3-methoxyphenyl) -5-mercaptotetrazole, and the like. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide
An amount of about ⁻² mol is preferable, and 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol is more preferable. When it is added to the silver halide emulsion layer in the coating liquid preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide.
It is more preferably x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used, but in particular, as a dye having absorption in the visible region,
The dyes of AI-1 to 11 described in JP-A-3-251840, page 308 are preferably used, and as the infrared absorbing dye, the general formula (I) described in JP-A1-280750, page 2, lower left column,
The compounds represented by the formulas (II) and (III) have preferable spectral characteristics and are preferable because they have no influence on the photographic characteristics of the silver halide photographic emulsion and there is no contamination due to residual color. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column. When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is combined with a yellow coupler, a magenta coupler and a cyan coupler to spectrally sensitize silver halide in a specific region of a wavelength range of 400 to 900 nm. It has a layer containing an emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, JP-A-3-25 can be used.
BS-1 to 8 described on page 28 of 1840 can be preferably used alone or in combination. As the green-sensitizing sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. The same publication as the red photosensitive sensitizing dye
RS-1 to 8 described on page 29 are preferably used.
Further, when image exposure is performed by infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye.
The dyes IRS-1 to 11 described on pages 6 to 8 of 5950 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes. The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone or dimethylformamide or water and adding it as a solution, or as a solid dispersion. Although it may be added, it is preferable to add it as a solid dispersion because the effect of the present invention is enhanced.

As a method for obtaining a solid dispersion of a sensitizing dye, other than a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high speed stirring type disperser, JP-A-58-105
No. 141, a method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system under the conditions of pH 6 to 8 and 60 to 80 ° C., the surface tension of 38 dyne described in Japanese Patent Publication No. 60-6496.
It is possible to use a method of dispersing in the presence of a surfactant, which is controlled to be not more than / cm.

As a dispersing device which can be used for preparing a dispersion liquid, for example, in addition to the high speed stirring type dispersing device shown in FIG. 1 of JP-A No. 4-125631, a ball mill, a sand mill, an ultrasonic dispersing device, etc. Can be mentioned.

When using these dispersing devices, as described in Japanese Patent Laid-Open No. 4-125632, a method such as performing a pretreatment such as dry pulverization in advance and then performing a wet dispersion may be adopted.

As the coupler used in the silver halide photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm is formed by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
General formula (CI) described in JP-A-4-114154, page 17,
The coupler represented by (C-II) may be mentioned.
Specific compounds are described in CC-1 to C on pages 18 to 21 of the publication.
The thing described as C-9 can be mentioned. The magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is described in JP-A
The general formula (M-I) and (M-
The coupler represented by II) can be mentioned. Specific compounds are described on pages 13 to 16 of the publication, MC-1 to MC-11.
Can be mentioned. Among them, MC-8 to M described in pages 15 to 16 of the same publication
C-11 is preferable because it is excellent in reproducing colors ranging from blue to purple and red, and is also excellent in descriptive power of details.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (Y-) described on page 8 of JP-A-4-114154.
The couplers represented by I) can be mentioned. Specific compounds are described in YC-1 to YC-9 on pages 9 to 11 of the same publication.
Can be mentioned. Among them, YC-8 and YC-9 described on page 11 of the same publication
Is preferable because it can reproduce a preferable yellow color. When the oil-in-water emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material according to the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. And a low-boiling point and / or water-soluble organic solvent are also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

The compound (d-1) described on page 33 of JP-A-4-114154 is used for the purpose of shifting the absorption wavelength of the color forming dye.
1) and compounds such as the compound (A'-1) described on page 35 of the same publication can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

As the support used in the silver halide photographic light-sensitive material of the present invention, any material may be used, and polyethylene coated paper containing white pigment, baryta paper, vinyl chloride sheet, polypropylene containing white pigment are used. ,
A polyethylene terephthalate support or the like can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina,
Alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like can be mentioned. The white pigment is preferably barium sulfate or titanium oxide. The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight or more as the content in the water-resistant resin layer. Is preferred, and more preferably 15% by weight or more. The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention can be determined according to JP-A-2-
It can be measured by the method described in Japanese Patent No. 28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and even more preferably 0.10 or less as the coefficient of variation described in the above publication.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the surface of the support, if necessary, and then directly or undercoat layer (adhesiveness of the surface of the support, Applied through one or more undercoat layers for improving antistatic properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties) Good.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

Further, in the silver halide photographic light-sensitive material according to the present invention, various hardeners are used for the purpose of preventing damage or dissolution of the film during processing. As these hardeners, many compounds such as epoxy compounds, aziridine compounds, acryloyl compounds, vinylsulfonyl compounds, chlorotriazine compounds are known, and the silver halide photographic light-sensitive material according to the present invention. Any known hardener can be preferably used for the above. Among these hardeners,
Carboxyl group-activating low-molecular hardeners are preferred because they have a fast-acting effect and the resulting coating strength is high.

To form a photographic image using the silver halide photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning. As the aromatic primary amine developing agent used in the present invention, known compounds can be used, but aminophenol and p-phenylenediamine compounds are preferable.
Particularly, an aromatic primary color developing agent is preferably used. To the color developing solution, known developer component compounds can be added in addition to the color developing agent. The development processing apparatus used for the development processing of the silver halide photographic light-sensitive material according to the present invention may be a roller transport type in which the light-sensitive material is sandwiched between the rollers arranged in the processing tank, and the belt may be a light-sensitive material. It may be an endless belt method of fixing and transporting, but a processing tank is formed in a slit shape, a processing solution is supplied to the processing tank and the photosensitive material is transported, and the processing solution is atomized. A spray method, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used.

[0077]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Magenta coupler (M-1) 17.5 g, additive (ST-3) 17.5 g, (ST-4) 14.9 g, high boiling organic solvent DIDP (di-i-decyl phthalate) 11.4 g and high boiling organic Solvent DBP (dibutyl phthalate) 11.4g
60 ml of ethyl acetate was added to and dissolved in 10% gelatin aqueous solution containing 15.0 ml of 15% surfactant (SU-1).
220 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was mixed with a silver halide emulsion (Em-G101) (containing 8.50 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second layer coating liquid is also the first
It was prepared in the same manner as the layer coating solution. Further, (H-1) was added to the second layer as a hardener. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

Sample 101 was prepared as described above. The layer structure is shown in Table 3 below.

[0082]

[Table 3]

[0083]

[Chemical 6]

SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,5,5, -Octafluoropentyl) sodium salt H-1: Tetrakis (vinylsulfonylmethyl) methane PVP: Polyvinylpyrrolidone (Preparation of high silver chloride monodisperse emulsion) 2% gelatin aqueous solution kept at 40 ℃ 1000ml The following (solution A) and (solution B) are pA
Controlled to g = 6.5 and pH = 3.0, added simultaneously over 30 minutes,
Furthermore, the following (solution C) and (solution D) have pAg = 7.3, pH
It was added simultaneously over 180 minutes while controlling to 5.5. At this time p
The Ag is controlled by the method described in JP-A-59-45437.
The H was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion (EMP-1) having a diameter of 0.40 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

(Preparation of green-sensitive silver halide emulsion) The following compounds were used in the above emulsion (EMP-1) at 55 ° C.
Chemical ripening to obtain a green-sensitive silver halide emulsion (Em-G
I got 101).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX STAB-1: 1- (3-acetamidofemil) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole

[0088]

[Chemical 7]

In the preparation of the above high silver chloride monodisperse emulsion (EMP-1), the exemplary metal compound (6) was added to (C liquid) in an amount of 5 × 10 ^-8 mol per mol of silver halide. Similarly, average particle size 0.40 μm, coefficient of variation (S / R) = 0.
07, Monodisperse cubic emulsion with silver chloride content of 99.5 mol% (EMP-
2) got.

Similarly, the above high silver chloride monodisperse emulsion (EMP-
In the preparation of 1), the sulfur group compound S- is exemplified in (C liquid).
2 was added in an amount of 2.5 × 10 ^-8 mol per mol of silver halide in the same manner as above, except that the average grain size was 0.40 μm, the coefficient of variation (S / R) = 0.07, and the content of silver chloride was 99.5 mol%. A dispersed cubic emulsion (EMP-3) was obtained.

Monodispersed cubic emulsions (EMP-4) to (EMP-31) were prepared in the same manner by adding the compounds and amounts of the metal compounds and sulfur group compounds shown in the table below.

[0092]

[Table 4]

[0093]

[Table 5]

Green-sensitive silver halide emulsion (Em-G101)
In the preparation of, the monodisperse cubic emulsion (EMP-1) was added to (EMP
MP-2) to (EMP-31) except that green-sensitive silver halide emulsions (Em-G102) to (Em-G13) were used.
1) was prepared. Samples 102 to 131 were prepared in the same manner as Sample 101 except that the green-sensitive silver halide emulsion (Em-G101) was replaced with the green-sensitive silver halide emulsions (Em-G102) to (Em-G130).

The above sample was subjected to optical wedge exposure with an exposure time of 0.5 seconds by an ordinary method, and then the following development treatment was carried out 30 minutes after the exposure. Also, set the exposure time after exposure to 30 minutes,
Optical wedge exposure was performed with the same exposure amount while changing to 0.05 and 5 seconds, and the following development processing was performed. Further, with respect to the sample having the exposure time of 0.5 seconds, the development treatment was performed with the time from the exposure to the development being 1 minute and 5 minutes.

The processing steps are shown below.

Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80ml / m ² Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120ml / m ² Water wash 30-34 ℃ 60 seconds 150ml / m ² Dry 60-80 ℃ 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had a pH of 10.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Fluorescence Whitening agent (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonium hydroxide (25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

The green density of the obtained sample was measured using a PDA-65 densitometer (manufactured by Konica Corporation). Sensitivity is density 0.
Defined based on the reciprocal of the exposure dose giving 75, exposure time 0.
For samples that were developed for 5 seconds and 30 minutes after exposure,
Expressed as a relative value with the sensitivity of Sample 101 as 1, exposure time 0.05
The samples exposed for 5 seconds and the samples developed for 1 minute and 5 minutes after exposure were expressed as relative values with the sensitivity of the sample processed at each exposure time of 0.5 seconds and 30 minutes after exposure as 100. . The results are shown in Tables 6 and 7.

[0102]

[Table 6]

[0103]

[Table 7]

As is clear from these results, the sample containing only the comparative metal compound has a small sensitivity variation due to the exposure time, but the sensitivity is low, and the sensitivity changes with the time from the exposure to the development processing. Is big. On the other hand, the sample containing only the sulfur group compound for comparison has a small change in sensitivity with respect to the time from the exposure to the development treatment, but has a low sensitivity and a large sensitivity variation due to the exposure time. A sample containing both a metal compound and a sulfur group compound but having a ratio of the total number of effective anion valences and the total number of effective cation valences outside the scope of the present invention was subjected to sensitivity fluctuation due to exposure time and exposure. There is no sample that satisfies both the sensitivity fluctuations with respect to the time from development to development processing. It can be seen that the sample of the present invention has small sensitivity variation due to exposure time and sensitivity variation with respect to the time from exposure to development processing, and has obtained these characteristics with high sensitivity.

Example 2 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing a surface-treated anatase type titanium oxide dispersed in a content of 15% by weight was laminated to prepare a reflective support. Each layer having the constitution shown below was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, dye image stabilizer (ST-2) 3.34 g, stain inhibitor (HQ-1) 0.33
g and high boiling point organic solvent (DBP) 5.0 g ethyl acetate 6
0 ml was added and dissolved, and this solution was added with 20% surfactant (SU-
1) A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of 10% gelatin aqueous solution containing 7.0 ml using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Moreover, (H-1) and (H-2) were added as a hardening agent. Surfactants (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted. The total amount of F-1 in each layer is 0.04g
/ M ² was added.

The layer structure is as shown in Tables 8 and 9 below.

[0108]

[Table 8]

[0109]

[Table 9]

[0110]

[Chemical 8]

[0111]

[Chemical 9]

[0112]

[Chemical 10]

[0113]

[Chemical 11]

[0114]

[Chemical 12]

DNP: dinonyl phthalate DOP: dioctyl phthalate H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium HQ-6: pt-octylphenol (Preparation of blue-sensitive silver halide emulsion) 2% kept at 40 ℃
The following (solution A) and (solution B) in 1000 ml of gelatin aqueous solution
Were simultaneously added over 30 minutes while controlling the pH to 6.5 and the pH to 3.0, and the following (solution C) and (solution D) were added to pAg = 7.
3. Simultaneously added over 180 minutes while controlling pH = 5.5.
At this time, the pH was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water added 200 ml (Solution B) Silver nitrate 10 g Water added 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size. A monodisperse cubic emulsion (EMP-32) having a diameter of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

The above emulsion was chemically ripened for 90 minutes at 55 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em
-B201) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole (Preparation method of red-sensitive silver halide emulsion) (solution A) and (B)
(Liquid) and the addition time of (C liquid) and (D liquid) were changed in the same manner as in (EMP-1), and the average particle size was 0.
A monodisperse cubic emulsion (EMP-33) having 50 μm, a coefficient of variation (S / R) = 0.08 and a silver chloride content of 99.5 mol% was obtained.

(EMP-33) was chemically ripened at 60 ° C. for 90 minutes using the following compound to obtain a red-sensitive silver halide emulsion (Em-R201).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX

[0121]

[Chemical 13]

Next, in the preparation of the monodisperse cubic crystal emulsion (EMP-32), the average particle size was 0.85 μm and the variation coefficient ( S
/R)=0.07 and a silver chloride content of 99.5 mol% were prepared as monodisperse cubic emulsions (EMP-34) to (EMP-41). A blue-sensitive silver halide emulsion (Em-B201) was prepared in the same manner as in the above except that the monodisperse cubic emulsion (EMP-32) was replaced with the monodisperse cubic emulsions (EMP-34) to (EMP-41). Silver Halide Emulsion (Em-B202) ~ (Em-
B209) was prepared. Next, a monodisperse cubic emulsion (EMP
-33), the compound and amount of
The same procedure as described above except that the monodisperse cubic emulsions (EMP-42) to (EMP-49) having an average particle size of 0.85 μm, a coefficient of variation (S / R) = 0.07 and a silver chloride content of 99.5 mol% were added. Prepared. A blue-sensitive silver halide emulsion (Em-R201) was prepared in the same manner except that the monodisperse cubic emulsion (EMP-33) was replaced with the monodisperse cubic emulsions (EMP-42) to (EMP-49). Silver halide emulsion (Em-R202)
~ (Em-R209) were prepared.

[0123]

[Table 10]

In the preparation of a multilayer silver halide photographic light-sensitive material, a blue-sensitive silver chlorobromide emulsion, a green-sensitive silver chlorobromide emulsion and a red-sensitive silver chlorobromide emulsion were sampled from Samples 201 to 211 as shown in Table 11 below. Was produced.

[0125]

[Table 11]

The above sample was subjected to optical wedge exposure with an exposure time of 0.5 seconds by an ordinary method, and then the following development treatment was carried out 30 minutes after the exposure. Also, set the exposure time after exposure to 30 minutes,
The development processing described in Example 2 was performed by performing optical wedge exposure with the same exposure amount while changing it to 0.05 and 5 seconds. Furthermore, exposure time 0.5
The second sample was subjected to a development treatment by setting the time from exposure to development to 1 minute or 5 minutes.

The blue, green and red densities of the obtained samples were measured using a PDA-65 densitometer (manufactured by Konica Corporation).
Blue, green and red sensitivities were defined based on the reciprocal of the exposure dose giving a density of 0.75 respectively. For blue, green and red sensitivities, the exposure time is 0.5 seconds, and for samples that were developed 30 minutes after exposure, the sensitivity of sample 201 is expressed as a relative value, and the exposure time is 0.05 seconds, 5 seconds. With respect to the sample exposed at 1, and the sample developed at 1 minute and 5 minutes after the exposure, the sensitivity of the sample processed at each exposure time of 0.5 seconds and 30 minutes after the exposure was represented as a relative value. The results are shown in Table 12.

[0128]

[Table 12]

A sample containing the metal compound of the present invention and the sulfur group compound and having a ratio of the total number of effective anion valences to the total number of effective cations within the range of the present invention was subjected to sensitivity fluctuation due to exposure time and exposure. It can be seen that the sensitivity variation with time from the time to the development processing is small and these characteristics are obtained with high sensitivity. It can be seen that the emulsion of the present invention produces an effect irrespective of the color sensitivity, and the effect is sufficiently obtained even in a multilayer silver halide photographic light-sensitive material.

[0130]

According to the present invention, a negative-working silver halide photographic emulsion capable of providing a silver halide photographic light-sensitive material having high sensitivity and small sensitivity fluctuations due to exposure time and sensitivity fluctuations from exposure to development is provided. I was able to.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/00 510

Claims (2)

[Claims] 1. At least one compound is added until the physical ripening of silver halide grains is completed, and at least one of the compounds is a group 8-10 metal or a group 12 transition metal of the periodic table. Lead, rhenium, molybdenum, tungsten,
It is a metal compound having chromium and gallium, and is characterized by containing silver halide grains in which the total effective anion valence of the added compound is 0.9 times or more and 1.35 times or less of the total effective cation valence. Negative type silver halide photographic emulsion. 2. At least 95 mol% of silver chloride is composed of silver chloride, and at least one sulfur group element simple substance or compound is added before the physical ripening of silver halide grain formation. Item 2. A negative type silver halide photographic emulsion as described in Item 1.